<p style="text-align: justify;">U okviru ove doktorske disertacije ispitana je mogućnost ekstrakcije bioaktivnih jedinjenja iz biljne pra&scaron;ine A. uva-ursi, koja nastaje kao sporedni proizvod u fabrici filter čaja. Za ekstrakciju bioaktivnih jedinjenja primenjene su različite tehnike ekstrakcije (klasična ekstrakcija, ultrazvučna ekstrakcija i ekstrakcija subkritičnom vodom), kao i različiti ekstragensi: voda na sobnoj temperaturi, 30-70% etanol i subkritična voda. Sadržaj bioaktivnih jedinjenja u ekstraktima ispitan je primenom odgovarajućih spektrofotometrijskih metoda i HPLC metode. U ekstrakciji biljne pra&scaron;ine A. uva-ursi detaljno je matematički analiziran uticaj procesnih parametara na ekstrakciju subkritičnom vodom bioaktivnih jedinjenja iz materijala ovog tipa i u tom smislu je posmatran uticaj temperature, vremena i dodatka kiseline, a takođe su određeni uslovi pri kojima je, primenom ove tehnike, moguće ostvariti maksimalnu ekstrakciju bioaktivnih jedinjenja od značaja. Pored toga prikazana je i mogućnost primene spray drying tehnike za su&scaron;enje tečnih i proizvodnju suvih ekstrakta A. uva-ursi u formi praha. Na kraju, na osnovu koncentracije bioaktivnih jedinjenja i njihovog delovanja, dat je predlog nekoliko novih preparata na bazi ekstrakata A. uva-ursi, u tečnoj i čvrstoj formi.</p> / <p>This dissertation investigated the possibility to extract bioactive compounds from A. uva-ursi herbal dust, which occurs as a by-product at the filter-tea<br />factory. Various extraction techniques (classical extraction, ultrasound assisted extraction and subcritical water extraction), were applied for the extraction of bioactive compounds, as well as different solvents: water at room temperature, 30-70% ethanol and subcritical water. The content of bioactive compounds in the extracts was investigated using appropriate spectrophotometric methods and the HPLC method. In the extraction of A. uva-ursi herbal dust a detailed mathematical analysis of the influence of process parameters on subcritical water extraction of bioactive compounds from this type of material was conducted. In this regard the influence of temperature, time and acid addition was observed and the conditions under which it is possible to achieve maximum extraction of significant bioactive compounds, by applying this technique, were determined. In addition, the possibility of applying the spray drying technique for drying the liquid and producing dry A. uva-ursi extracts in the form of powder is also presented. Eventually, based on the concentration of the bioactive compounds and their activity, a proposal for a several new preparations in liquid and solid form, based on A. uva-ursi extracts is given.</p>

The work presented in this thesis concerns the development and evaluation of new methods of sampling and analysis of organic pollutants in the indoor and outdoor environment. In Paper I, the development of a new method was reported for the determination of the brominated flame retardant tetrabromobisphenol A (TBBPA) in air using sampling with glass fiber filter and polyurethane foam (PUF), ultrasonic solvent extraction and liquid chromatography coupled to electrospray ionisation mass spectrometry (LC-ESI/MS). The MS fragmentation mechanism of TBBPA was thoroughly investigated and different acquisition modes were evaluated to achieve the most sensitive and selective detection. In Papers II and III, the potential use of Empore SPE membranes was evaluated for air sampling of volatile, semi-volatile and particle-associated organic compounds. Breakthrough studies conducted for 24h at air flows of 10- 20 L/min showed that the SPE membranes efficiently retains volatile and semi-volatile organophosphate esters and particles &gt;10 nm. Effort was invested in the development of fast and environmental friendly methods, with low cost, for sample clean up and analysis. In Paper II, the sample preparation technique was dynamic solvent extraction with methanol coupled to LC-ESI/MS. The total run time per sample, including both extraction and separation, was less than 34 min, consuming only 1.6mL methanol. In Paper III, efficiency of selective extraction of polycyclic aromatic hydrocarbons from particulate matter sampled with Empore SPE membranes, using dynamic subcritical water extraction (DSWE) was investigated. Acceptable recoveries of the investigated compounds from reference material (SRM 1649a) were achieved. In Paper IV, the application of dynamic solid phase micro-extraction (SPME) air sampling was evaluated using, gas chromatography/positive ion chemical ionisation (GC/PICI) and tandem-MS detection for the determination of organophosphate esters in work environment.

Orientador: Ciro Antonio Rosolem / Banca: Dirceu Maximino Fernandes / Banca: José Carlos Casagrande / Resumo: Em algumas condições não se têm obtido correlações entre os teores de B do solo, extraído com água quente, o teor de boro na planta e a produtividade da soja no Estado do Mato Grosso, mais precisamente na região de Campo Novo do Parecis. Sabe-se que o boro é um nutriente fortemente adsorvido nas partículas minerais do solo. Objetivou-se com este trabalho submeter amostras de solo de uma determinada área de estudo, na qual foi cultivada soja por três anos consecutivos e posteriormente cultivado algodão, a diferentes métodos de extração de boro, a fim de se estabelecer correlações entre a dose de boro na planta, a dose de nutriente aplicada e o teor de boro no solo disponível às plantas e, ainda, com a produtividade da soja. Amostras de solo, cultivadas com soja, coletadas por ocasião da condução do experimento no campo, foram analisadas quanto à concentração de B extraída pelos métodos: água quente modificado com solução de BaCl2 1,25 g L-1 (recomendado e chamado de método da água quente pelo IAC); água quente modificado com solução de CaCl2 0,01 mol L-1,a quente e água quente tradicional (o qual é preconizado por muitos autores como o método oficial) para dessa forma, tentar quantificar a real disponibilidade de boro neste solo, caracterizado como um LATOSSOLO VERMELHO AMARELO (LVA), possibilitando a determinação de um nível crítico. Ainda, durante o período de condução do trabalho, foi feito um estudo de adsorção de B nas amostras, e um estudo do comportamento da lixiviação do nutriente em colunas de solo, procurando verificar o efeito das adubações na dinâmica do nutriente. Em relação aos métodos de extração de boro no solo, o CaCl2 foi o que apresentou correlação positiva e significativa com o boro presente no tecido vegetal nos três anos agrícolas. Os métodos do BaCl2 e ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In some conditions, doesn't have obtained correlations among boron content in soil, boron extracted by hot water, boron content in plants and soybean productivity in a region (Campo Novo do Parecis) of the state of Mato Grosso/Brazil. This work was carried out to submit soil samples from determined area of study where was tillage soybean for three subsequent years and after tillage cotton, to differents extraction methods by boron with the aim to establish correlations among, amount of boron content in plants, amount of nutrient putted in soil, boron content in soil disponible to plants and the productivity. Soil samples obtained during the conduction of experiment on field were analyzed to predict the amount of boron in soil by the methods: hot water modified with BaCl2 solution (recommended and called by hot water from IAC - Instituto Agronômico de Campinas/SP-Brazil), hot water modified CaCl2 0,01 mol L-1 solution and hot water traditional (which is preconized by many authors like the official method) to this way try to quantify the real situation of boron disponibility in this soil, characterized like a Yellow Red Latossol, to take the determination of a critical level. During the conduction period of this work was made an adsorption study in the samples, and still a study of boron leaching behavior in soil columns, to verify fertilizer effect in nutrient dynamic. The extraction method with CaCl2 presented positive and significative correlation with boron present in soybean leaves on three subsequent farm work years. BaCl2 method and hot water traditional also presented positives and significatives correlations each one in two farm work years, this results were expected in function of similarity among three methods, it's an evidence that there is a method with capacity to predict boron disponibility in soils of Mato Grosso... (Complete abstract, click eletronic address below) / Mestre

Spruce Bark contains several fundamental main substances; lignin, non-cellulose polysaccharides, cellulose and extractives. This undergraduate study focuses on developing a process to extract each of these components from spruce bark using a biorefinery concept, with a main focus on extracting lignin without degradation. The purpose of the Bark biorefinery concept is to contribute to a circular bioeconomy, by making use of natural resources. With extended research on the area, it will be possible to produce polymers, green chemicals and biofuel from the components in bark.  This report covers the extraction of the bark components with soxhlet extraction, Hot-water extraction, organosolv extraction and peracetic acid delignification. The extraction was made on two samples, matchstick-sized bark (MS) and 20 mesh-sized bark with a diameter of 0.8 mm (20M). The purpose was to be able to compare the efficiency of the extraction between the two samples. Afterwards, the characterisation of extracts and residue was executed with carbohydrate analysis, 2D HSQC-NMR and FTIR-analysis.  The results showed that a smaller particle size led to more efficient extractions of all components as well as more pure extract solutions. Lignin concentration determinations of samples at each step showed that a significant amount of lignin was lost prior to the organosolv extraction. Future research should look into ways to reduce this loss in order to increase the lignin yield. The findings in the FTIR and NMR analyses correlates with what could be seen in other reports, discussing similar subjects. For upscaling of this process, future research should go toward optimization of all extraction methods in order to make an upscaling of the process economically viable.

<p>U okviru ove doktorske disertacije ispitane su i<br />poređene različite ekstrakcione tehnike korena<br />gaveza, lista crnog duda i peteljki tre&scaron;nje. Poređene<br />su konvencionalne i savremene ekstrakcione<br />tehnike i izvedena je optimizacija ekstrakcionih<br />postupaka s ciljem dobijanja ekstrakata ispitivanih<br />biljnih vrsta sa najvećom bioaktivno&scaron;ću. Za svaku<br />ekstrakcionu tehniku ispitan je uticaj najznačajnijih<br />parametara: maceracija (rastvarač i vreme<br />ekstrakcije), ubrzana ekstrakcija (temperatura i<br />rastvarač), supekritična ekstrakcija (pritisak i<br />koncentracija ko-rastvarača) i ekstrakcija<br />subkritičnom vodom (temperatura, pritisak, vreme<br />ekstrakcije i brzina me&scaron;anja). Ekstrakcija polifenola<br />korena gaveza, lista crnog duda i peteljki tre&scaron;nje je<br />bila najefikasnija ekstrakcijom subkritičnom<br />vodom. Primenjene su tehnika visokopritisne tečne<br />hromatografije spregnute sa masenom<br />spektrometrijom uz primenu različitih masenih<br />analizatora, masenog analizatora na bazi vremena<br />preleta jona i tandema kvadrupolnog i analizatora<br />na bazi vremena preleta jona. Za karakterizaciju<br />dobijenih ekstrakata instrumentalnom analizom su<br />određene kvalitativne i kvantitativne karakteristike dobijenih ekstrakata korena gaveza, lista crnog duda i peteljki tre&scaron;nje. HPLC-ESI-QTOF-MS/MS analizom ekstrakata identifikovano je vi&scaron;e od 27 novih jedinjenja različitih hemijskih klasa u svakom od ispitivanih biljnih matriksa.</p> / <p>Within the scope of this doctoral dissertation,<br />different extraction techniques of comfrey root,<br />black mulberry leaves and sweet cherry stems were<br />applied and compared. Conventional and novel<br />extraction techniques were optimized and<br />compared in order to obtain plant extracts with the<br />highest content of bioactive compounds. The<br />influence of the most important parameters was<br />investigated for each extraction technique:<br />maceration (solvent and extraction time),<br />accelerated solvent extraction (temperature and<br />solvent), supercritical fluid extraction (co-solvent<br />percentage and pressure) and subcritical water<br />extraction (temperature, pressure, extraction time<br />and agitation rate). Extraction of polyphenolic<br />compounds from comfrey root, black mulberry<br />leaves and sweet cherry stems was the most<br />effective using subcritical water. High-pressure<br />liquid chromatography coupled to mass<br />spectrometry techniques using time-of-flight and<br />quadrupole-time-of-flight mass analyzers have<br />been used to characterize bioactive compounds.<br />Qualitative and quantitative characteristics of the<br />obtained comfrey root, black mulberry leaves and sweet cherry stem extracts were determined. HPLC-ESI-QTOF-MS/MS revealed the presence of more than 27 compounds of different chemical classes that have been identified for the first time in&nbsp; the plant matrix.</p>

Les régions de Midi-Pyrénées (France) et de Chongqing (Chine) sont riches en plantes aromatiques et médicinales dites oubliées (ou médiévales). Afin de valoriser pleinement les différentes bio-molécules extractibles de ces plantes, le concept de MAP-raffinerie a été créé et appliqué à une sélection de plantes issues de ces deux régions. Plusieurs technologies d’extraction utilisant l’eau comme solvant vert (hydrodistillation, distillation à la vapeur et extraction par eau sub-critique) ont ainsi été employées et leur impact tant sur la composition des huiles essentielles que sur la récupération des molécules anti-oxydantes a été évalué. Dans un premier temps, une liste de plantes aromatiques et médicinales oubliées, voire sous-utilisées dans les deux régions a été établie selon des règles de sélection prédéfinies. Six plantes modèles de la région de Midi-Pyrénées (Tussilago farfara L., Calendula arvensis L., Robinia pseudoacacia L., Geranium robertianum L., Cytisus scoparius L. et Spartium junceum L.) et trois plantes de la région de Chongqing (Tussilago farfara L., Citrus aurantium L. et Saussurea costus) ont finalement été retenues. Puis, le concept de MAP-raffinerie a été appliqué à ces plantes afin d’étudier leur possible valorisation globale. L’étude des compositions chimiques des extraits volatils des racines de Tussilago farfara L. et de Calendula arvensis L., ainsi que des boutons de fleurs de Spartium junceum L. a été réalisée par GC et GC-MS pour la première fois. Les principaux composés chimiques dans l’extrait volatil de racines de Tussilago farfara L. étaient des hydrocarbures sesquiterpéniques et des composés aliphatiques tandis que les principaux composés chimiques dans l’extrait volatil de racines de Calendula arvensis L. étaient des sesquiterpènes oxygénés, des monoterpènes oxygénés et des diterpènes oxygénés. L’extrait volatil de boutons de fleurs de Spartium junceum L. était principalement composé de composés aliphatiques. Par ailleurs, les résultats de l’évaluation des capacités anti-oxydantes des extraits (par les tests DPPH, ABTS, FRAP, ORAC et Folin-Ciocalteu) ont montrés que plusieurs plantes comme Cytisus scoparius L., Tussilago farfara L., Citrus aurantium L. ou Robinia pseudoacacia L. pourraient être des sources potentielles d’anti-oxydants naturels. D’un point de vue technologique, les comparaisons de l’utilisation de l’hydrodistillation (HD), de la distillation à la vapeur (SD) et de l’extraction par eau sub-critique (SWE) ont montrées que si la HD et la SD ont des effets limités sur la composition des huiles essentielles, la HD semble être une méthode plus efficace pour la récupération des composés anti-oxydants à partir des résidus de distillation que la SD tandis que la SWE s’avère être une technologie prometteuse pour l’extraction directe de ces molécules à partir des plantes. Si la composition minérale de l’eau lors de l’hydrodistillation n’a que des effets très limités sur les rendements d’extraction, les teneurs en ions calcium et bicarbonate des eaux ont par contre des effets décroissants significatifs sur la capacité anti-oxydante et sur la teneur phénolique totale des extraits aqueux et méthanoliques. Au vue de ces résultats, un concept amélioré de MAP-raffinerie a été développé en intégrant une extraction à l’eau sub-critique pour l’extraction des composés anti-oxydants des résidus d’extraction primaire. Selon ce nouveau concept, cinq extraits peuvent être obtenus à partir des matières végétales: un extrait volatil, un extrait aqueux, un extrait méthanolique, un extrait à l’eau sub-critique et in fine un résidu solide. Les premiers résultats ont montrés que la "MAP-raffinerie améliorée" augmente de manière significative la récupération des antioxydants par rapport à la MAP-raffinerie originale et permet d’envisager une valorisation plus facile du résidu solide en agro-matériaux du fait de sa faible teneur en eau résiduelle. / In both Midi-Pyrénées region (France) and Chongqing region (China), there are rich and underutilized medicinal and aromatic plants (MAP). Aiming at fully exploiting different molecules in these plants, the concept of MAP-refinery was developed and applied to several underutilized medicinal and aromatic plants in these two regions. Several water-based green extraction technologies of natural products (e.g. hydrodistillation, steam distillation and subcritical water extraction) were also investigated to look at their effects on essential oil composition and antioxidants recovery from selected plants. Firstly, lists of forgotten or underutilized medicinal and aromatic plants in both regions were established according to the rules of selection. From the lists, six plants in the Midi-Pyrénées region (Tussilago farfara L., Calendula arvensis L., Robinia pseudoacacia L., Geranium robertianum L., Cytisus scoparius L. and Spartium junceum L.) and three plants in the Chongqing region (Tussilago farfara L., Citrum aurantium L. and Saussurea costus) were finally selected for investigations. Then the MAP-refinery was applied to the selected plants in two regions in order to realise their global valorisation. Volatile extracts composition in the roots of Tussilago farfara L. and Calendula arvensis L., as well as flower buds of Spartium junceum L. were firstly investigated. The main chemical compounds in volatile extract from Tussilago farfara L. roots were sesquiterpene hydrocarbons and aliphatic compounds while main chemical compounds in volatile extract from Calendula arvensis L. roots were oxygenated sesquiterpenes, oxygenated monoterpenes and oxygenated diterpenes. The volatile extract from flower buds of Spartium junceum L. was mainly composed of aliphatic compounds. Antioxidant capacity evaluation results (by DPPH, ABTS, FRAC, ORAC and Folin-Ciocalteu tests) showed that several plant samples like Cytisus scoparius L., Tussilago farfara L., Citrum aurantium L. and Robinia pseudoacacia L. could be potential sources of natural antioxidants. Comparisons of hydrodistillation (HD), steam distillation (SD) and subcritical water extraction (SWE) showed that HD and SD had limited effects on essential oil composition but HD, SD and SWE had significant impacts on the recovery of antioxidants. Hydrodistillation seemed to be a better method for recovery of antioxidant compounds from residues of distillation than steam distillation. However, SWE appeared to be a more efficient method for direct extraction of antioxidant molecules (or phenolic compounds) from plants. In the hydrodistillation process, mineral contents in water were found to have very limited effects on yields of extracts but calcium and bicarbonate ions, had significant decreasing effects on antioxidant capacity and total phenolic content of both aqueous and methanolic extracts. Finally, an improved MAP-refinery was developed. Subcritical water was used for further extraction of antioxidant compounds from residues in original MAP-refinery. In this way, five parts could be obtained from plant materials: volatile extract, aqueous extract, methanolic extract, subcritical water extract and the final residue. The results showed that the improved MAP-refinery significantly increased the recovery of antioxidants compared with original MAP-refinery. This promising process will also allow a better valorisation of the final solid residue due to the lower content of residual water.